Certain oxyalkylated n-methyl glucamines and method of making same



1959 M. DE GROOTE ETAL 2,917,505

CERTAIN OXYALKYLATED N-METHYL GLUCAMINES AND METHOD OF MAKING SAME Original Filed Aug. 10, 1954 BINARY REACTION PRODUCT FOR OXYETH YLATI ON METHYLGLUCAMINE DD BINARY REACTION PRODUCT FOR OXYPROPYLATION United States Patent F CERTAIN OXYALKYLATED N-METHYL GLUCA- MINES AND METHOD OF MAKING SAME Melvin de Groote, St. Louis, and Owen H. Pettingil], Kirkwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware Original application August 10, 1954, Serial No. 448,923. l6)ivided and this application April 10, 1957, Serial No.

7 Claims. Cl. 260-211) More specifically then, the present invention is con cerned with a cogeneric mixture of a homologous series of glycol ethers of N-methylglucamine. The cogeneric mixture is derived exclusively from N-methylglucamine, propylene oxide and ethylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum N-methylglucarnine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines connecting A, B, F, E. Our preference by far is to use the compositions which represent less than one-half of this total area, to wit, the smaller trapezoid A, B, D, C. Reference to methylglucamine means N-methylglucarnine in all instances.

It is immaterial as to whether one reacts the amine with propylene oxide first and then with ethylene oxide, or with ethylene oxide and then with propylene oxide; or, for that matter, one may employ a mixture of the two oxides; or, if desired, one may add a small amount of ethylene oxide, then propylene oxide, and then more ethylene oxide.

Referring to the hereto attached drawing it is simplified by noting that one may react methylglucamine with enough ethylene oxide so the binary reaction product falls Within the mixture identified by the line CC DD on the extremity of the graph which shows combinations derived solely from methylglucamine and ethylene oxide. After obtaining such binary reaction product it can then be reacted with propylene oxide so as to bring it within the area of the trapezoid A, B, F, E, or preferably within the smaller trapezoid A, B, D, C.

Similarly, one can produce a binary reaction product from methylglucarnine and propylene oxide as identified by the comparable line AA-BB and subject this reacplies particularly to reactions involving monoepoxides 2,917,505 Patented Dec. 15, 1959 ICC tion product to oxyethylation so as to bring the composition Within the area of the trapezoid and preferably within the area of the small trapezoid A, B, D, C.

The products of the present invention are also useful for various purposes other than the resolution of petroleum emulsions of the water-in-oil type. The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as gennicides, insecticides, emulsifying agents as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

For the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface-active'materialsare effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated deriva-' generally xylene, is described as an index of surface activity.

The above mentioned test, i.e., a conventional emulsification test, simply means that the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water insoluble or even a fraction of a water-soluble hydrocarbon solvent and that when shaken with water the product may remain in the nonaqueous solvent or, for that matter,-it may pass into the aqueous solvent. In other words, al-

though it is xylene soluble, for example, it may also be' water soluble to an equal or greater degree.

For purpose of convenience, what is said hereinafter will be divided into four parts:

Part 1 is concerned with the oxyalkylation of N-methyl glucamine in a general way;

Part 2 is concerned with the oxyalkylation of N-methylgulcamine using two different oxides, i.e., propylene oxide and ethylene oxide so as to produce derivatives fallingwithin said compositional limits as previously described and noted hereinafter in detail;

Part 3 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of'the previously described chemical compounds; and

Part 4 is concerned with uses for the products hereinv including applications other than those involving the resolution ofdescribed either as such or after modification,

petroleum emulsions of the water-in-oil type.

} PART 1 v The oxyalkylation of amines is well known. This aphaving not over 4 carbon atoms, such as ethylene oxide and propylene oxide. As to the oxyalkylation of a monoamine such as cyclohexylamine, see U.S. Patent. No.

2,626,922, dated January 27, 1953, to De Groote. Astob In said patent such 3 the'oxyalkylation of 'a polyarnine, see US. Patent No. 2,552,530, dated May 15, 1951, to De Groote.

The oxyalkylation of an amine is comparable to other well known oxyalkylations and under certain conditions may require variation. There is no problem if the amine 1s a liquid or if it is xylene-soluble or soluble in an equivalent solvent, or can be melted and reacted at the melting point. In the case of rnethylglucamine the product is a solid and one of the most satisfactory procedures 1s to use a slurry of the finely powdered material in xylene comparable to the oxyalkylation of sorbitol. As to thisprocedure, see Example A in US. Patent No. 2,552,528, dated May 15, 1951, to De Groote. Since methylglucamine melts at l28129 C. it is obvious'that although one starts with a solid that the product is a liquid at the reaction temperatures employed in the majority of instances.

In order to illustrate why the herein contemplated compounds or said products are cogeneric mixtures and not single chemical compounds, and why they must be described in terms of manufacture, and molal ratio or percentage ratio of reactants, reference is made to a monohydric alcohol. alcohol having 5 reactive hydrogen atoms attached to oxygen and also one attached to nitrogen. Thus, for the present purpose it might be considered the same as an,

amino alcohol having 6 hydroxyl radicals. However, for the moment, one can forget the hydrogen atom attached to nitrogen and even'the plurality, of hydroxyl radicals and simply consider what happens when a monohydric alcohol is subjected to oxyalkylation.

If one selects any hydroxylated compound and subjects'such compound to oxyalkylation, such as oxyethylation or oxypropylation, it becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. .This is particularly true where the amount of oxide added is comparatively large,

for instance ,10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent which. for sake of convenience, may be indicated as RO(C H O) ,,H. Instead, one obtains a cogeneric mixture of closely related homologous compounds in which the formula may be shown as the following: RO(C H.,O),,H, wherein n, as far as the statistical average goes, is'30, but the individual members present in significant amount may very from instances where n has a value of 25 and perhaps less, to a point where 11' may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i.e., the ability to describe how'to make the product underv consideration and how to repeat such production time after time without difi'iculty, it is necessary to resort to some other method of description.

What has been said in regard to a monohydric compound of course is multiplied many times in the case of'a polyhydric compound such as methylglucamine.

Although acid catalysts are used in oxyalkylations they areused to a lesser extent in the oxyalkylations of basic amines and the like. Under such circumstances one may have to use enough of the acidic catalyst to neutralize the basicity of the product and convert into a salt. This Methylglucamine is a polyhydric is not true where certain clays or prepared earths are used which act as acidic catalysts. In any event, it 15 our preference to use basic catalysts such as caustic soda, sodium methylate, or the like.

PART 2 in the literature. If the product is a liquid such as triethanolamine one can proceed to treat with an alkylene oxide such as ethylene oxide, propylene oxide, or'butylene oxide, at least in the early stages if desired without adding any catalyst. Generally speaking, if oxyalkylation is rather extensive as in the present instance, one requlres a catalyst afterthe initial stage and it is just as simple to add it from the very beginning. If the amine is a solid at ordinary temperature and this is true in regard to methylglucamine, one can readily follow the procedure of using a slurry in the same manner that is employed 1n connection with other solids although not necessarily nitrogen-containing. Reference is made to products such as sorbitol, sucrose, glucose, pentaerythritol, dipentaerythritol, etc. As previously pointed out methylglu'cam me is apt to be a liquid at the reaction temperature which usually is above the melting point. 7

Specific reference is made to the instant application which is concerned with ethylene oxide, and propylene oxide, or the equivalents. Actually, whether one uses ethylene oxide or butylene oxide or, for that matter, propylene oxide, one preferably starts with either the powdered solid suspendedas a slurry in xylene or a SllIll--' lar inactive solvent; or one employs an alkylene car bonate such as ethylene carbonate, butylene carbonate, or propylene carbonate, for the initial oxyalkylatiou. When such initial oxyalkylation has gone far enough to convert the solid mass into a product which. is at least liquid at'oxya'lkylation temperature it can be subjected to the oxides as differentiated from the carbonates. The carbonates, of course, cost more than the oxides.

In any event, any one of a number of well known procedures maybe employed and reference has been made to US. Patent No. 2,652,394 dated September 15, 1953, to De Groote. This particular patent happens to be concerned with sucrose but, as a matter of fact, one can just as readily substitute methylglucamine and the reaction will go just as rapidly and, in fact, perhaps more rapidly than with sucrose. Referring to said aforementioned patent, the same procedure using propylene oxide, or ethylene oxide, can be employed simply using mixed oxides instead.

It is not believed any examples are necessary to illustrate such well known procedure but for purpose of illus- The reactionvessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 4 liters. The stirrer operated at a speed of approximately 250 rpm. There were charged into the autoclave 500 grams of methylglycarnine, 300 grams of xylene, and 15 grams of sodium methylate; The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature was allowed to rise to approximately 152 C. At this particular time the addition ofpropylene oxide was stated. Propylene oxide wasadded continuously at such speed that it was absorbed by the reaction as added. The amountadded in thisoperationwas 15 00..grams. The time required to add the propylene oxide was two hours. During this period the temperature was maintained at to C., using cooling water through the inner coils when neces ayeivgsos mum pressure during the reaction was 50 pounds per square inch. Ignoring the xlyene and sodium methylate and considering only the methylglucamine for conventions and-subsequently subjected to joint oxyalkylation so as to obtain limits. In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that methylglucamine were used. Note what has been said previously .as tothe melting point of methylglucamine.

' In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The two oxides can be mixed together in suitable propor- 75' ience, the resultant product represents 3 parts by weight of 5 one cannot determine the exact location of the propylene propylene oxide to one part by weight of methyloxide or ethylene oxide groups. In such instances the glucamine. The xylene present represented approximateprocedure again is identically the same as previously dely .6 of one part by weight. scribed and, as a matter of fact, we have used such methods in connection with methylglucamine; Example 20 Actually, methylglucamine'at times may contain a trace of moisture. Our preference is to preparethe slurry with The .reactlon. mass wasfransferreq to a larger autoclave an excess of xylene and distill off a part of the xylene (capacity liters). Wlthout addlng any more solvent so as to remove any trace of water and then flush out or any more Xylene the procedure was rfapeated so as the mass with nitrogen. Even so, there may be a few to another 1500 grams 9 PwPy1.e1.1e oxide 15 tenths of a percent of moisture remain although at times stantlany the same operaitng condltlons but requmng examination indicates at the most it is merely a trace. gr hours for the i At the end this stelp As previously pointed out the simplest procedure of 6 ran}; f zfi f i 6 to 1 (ratio propy all is to prepare a binary reaction product of ethylene me on e 0 me y g ucamme) oxide on the one hand or methylglucamine and propylene Examp 16 3a 20 oxide on the other hand, and react with the other oxide. Note line CCDD which indicates that in the binary I In a third step instead of adding 1500 grams of 1 reaction product obtained from methylglucamine and ene oxide, 1625 grams were added. The reaction slowed ethylene oxlde one elflploys approxmyately 665% to up and required approximately 6 hours, using the same 955% of ethylene oX1d e and approxlmately 35% operating temperatures and pressures. The ratio at the -t of methylghlealnlneend of the third step was 9.25 parts by weight of propyl- Similarly, If one refers to the llne 1t Ineans one oxide pcr Weight of methylglucamine. one would employ from 1.95% of methylglucamine up to 14.3% of methylglucamine and from 85.7% of pro- Example 4a pylene oxide up to 98.05% of propylene oxide. Actually, in other operations we have proceeded to At the end of this p the autoclave Was opened and do as follows: Mixed the methylglucamine with an aroan additional 5 grams of Sodium methylate added, the matic petroleum solvent and with powdered caustic soda. autoclave flushed out as before, and the fourth and final W h irr d this mixture at. 125 to 130 C. for a oxyalkylation Completed, using 1625 grams of P py short period of time, approximately one-half hour, flushed oxide, and the oxyalkylation W s Complete Within 3% 35 out with nitrogen, and then subjected to vacuum soas hours using the Same temperatures range and Pressure to eliminate any moisture. We then started to oxyproas p i? end of the reaction the prodtlet pylate and continued until oxypropylation was complete represented approxlmately -5 parts of p py OXlde and then immediately followed with ethylene oxide. 'In y Weight to one P l t of methylglucamine these examples the amount of materials used are indicated Having obtained oxypropylated methylglucamine the 40 in pounds, and in each instance, .of course, a suitable Products Were Subjected to oxyethylation 1n a manner size autoclave was used. Although the oxyalkylation comparable to the oxyethylation of triethanolalmne, or started under vacuum the maximum pressure at any i for t matter, in the Same Way that oxypfopylated was about 10 to 15 pounds. An eflicient agitating device sucrose i Subjected to oxyethylation in the manner was used and stirring speed was approximately 350 r.p.m. scribed i Patent 2,652,394, dated September These data covering nine oxyalkylations are included in 1953, to De Groote- Indeed, the Procedure is Table I, immediately following. The time periods are Pafatively mp for the reason t one 15 Working With shown. Incidentally, we have repeated these same opera- 3 liquid and also that ethylene oxide is more reactive tions using ethylene oxide first and then propylene oxide than propylene oxide. As aresult, using the sam am unt and we have also mixed the two oxides and completed of catalyst one can oxyethylate more rapidly than usually the same nine oxyalkylations under substantially the same at a lower pressure. conditions. 7 i TABLE I High- Ethy- Max Methyl- Bolling Caustic Propylene lene Time, Temp., Press, Ex. Nos. glucamine, Aromatic Soda, Oxide, Oxide, Hrs. 0. lbs. per h lbs. Petroleum lbs. Lbs. Lbs. sq. in.

Solvent The same procedure using aslurry of methylglucamine Referring again to the ratio of the initial reactants in xylene was compiled in connection with ethylene oxide based on the trapezoid in attached drawing it will be and the same mixture on a percentage basis was obtained noted that we have calculated the percentage of the three as in the above examples where propylene oxide and initial reactants for the points A, B,'C, D, E, and F,

and Nos. 1 through 14, inclusive. culated initial binary mixtures corresponding in essence to the lines CC-DD and AA-BB, all of which appears in self-explanatory form in Table II, immediately following.

products coming within the specified,

We have also cal- TABLE D.

Tertiary Mixture, Percent Basis Binary Intermediate Mixtures, Percent Basis Points on Boundary of Area Methyl- Propylene Ethylene Methyl- Propylene Methyl- Ethylene glueamine Oxide Oxide glucamine Oxide glucamine Oxide Aspreviously pointed out, the oxyalkylation of methylglucamine or similar hydroxylated polyamines has been described in the literature and is described also in detail above. All one need do is employ such conventional oxyalkylation procedure to obtain products corresponding to the compositions as defined. Attention is again directed to the fact that one need not add the entire amount of either oxide at one time but that a small portion of one could be added and then another small portion of the other, and the process repeated.

For purpose of illustration we have prepared examples in three different ways corresponding to the compositions on the drawing. In the first series propylene oxide and ethylene oxide were mixed; this series'is indicated as An, Ba, etc., through and including 14a; in the second series propylene oxide was used first followed by ethylene oxide and this series is indicated as Ab, Eb, etc., through and including 14b; and finally in a third series, ethylene oxide was used first followed by propylene oxide and this series is indicated as Ac, Bc, etc., through and including 14c.

TABLE III Composition Composition Composition Where Pro- Where Ethyl- Composition Correspond- Where Oxides pylene Oxide ene Oxide ing to Following Point Are Mixed Used First Used First Prior to Oxy- Followed by Followed by alkylation Ethylene Propylene Oxide Oxide Aa Ab Ac Ba B!) Be On. Cb Cc De D!) De Ea Eb Ec Fa Fb Fc 1a 1b 10 2a 2b 2c 3a 3b 3e 4a 4b 4e 5a 5b 5e 6a 6b 60 7a 7b 70 8a 8b 8e 9a 9b 9c 10a 10b 10c 11a 11b 11c 12a 12b 12c 13a 13b 130 14a 14b 140 The products obtained by the above procedure usually show some color varying from a light amber to a pale straw. They can be bleached in the usual fashion using bleaching clays, charcoal, or an organic bleach, such as peroxide or peracetic acid, or the like.

There are certain variants which can be employed without detracting from the metes and bounds of the invention, but for all practical purposes there is nothing to be gained by such variants and the result is merely For instance, any one of the two oxides a minor percentage. and'usually to a very small degree, by oxide which would introduce substantially the same group along with a side chain, for instance, one could employ glycidyl methyl ether, glycidyl ethyl ether, glycidyl isopropyl ether, or the like.

In the hereto appended claims reference has been made to glycol ethers of methylglucamine. Actually it well may be that the products should be referred to as polyol ethers of methylglucamine in order to emphasize the fact that the final products of reaction have more than increased cost. can be replaced to two hydroxyl radicals. However, the products may be.

considered as hypothetically derived by reaction of methylglucamine with the glycols, such as ethylene glycol, bu-

tylene glycol, propylene glycol, or polyglycols. For this reason there seems to be a preference to use the terminology glycol ethers of methylglucamine.

PART 3 reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 511 herein described.

PART 4 The compounds derived in the manner described may be used as such for breaking petroleum emulsions of the water-in-oil type. They also can be converted into derivatives of the kind subsequently described which also may be used for this same purpose. Such derivatives are useful for other purposes including the same purpose for which the herein described products are eifective. The herein described products may be used for various purposes where detergents, common solvents, emulsifiers, and the like are used. They may be used as lubricants and as additives to fluids used in hydraulic brake systems; they may be used as emulsifying agents to emulsify o1 remove greases or dirt; they may be used in the manufacture of a variety of other materials such as soluble oils, insecticide sprays, etc.

These products may actants as chemical intermediates, for instance, with various diepoxides or polyepoxides. They may be combined with a number of other monoepoxides, such as epichlorohydrin, styrene oxide, glycide and methylglycide. They may be reacted with allyl glycidyl ether, glycidyl isopropyl ether, and glycidyl phenyl ether.

Furthermore, such products may be reacted with glycidly butyl ether be combined with a variety of re-- 9 alkylene imines, such as ethylene irnine or propylene imine, to produce cation-active materials. Instead of an .imine, one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure HzCN wherein R and R" are alkyl groups.

The products may be combined with carboxy acids such as higher fatty'acids so as to change their characteristics or with polycarboxy acids, such as diglycolic, maleic acid, phthalic acid, succinic acid, and the like, to give resins, soft polymers, or fractional esters which are essentially monomeric. Such products and others herein described, may all be used for the resolution of petroleum emulsions of the water-in-oil type. The products without further reaction are particularly valuable as additives for lubricating oils which are derived from sources other than petroleum.

The herein described products and the derivatives thereof are particularly valuable in flooding processes for recovery of oil from subterranean oil-bearing strata when employed in the manner described in US. Patent No. 2,233,381, dated February 25, 1941, to De Groote and Keiser.

In a trapezoid such as A, B, D, C, the area can be divided conveniently into five portions by first drawing two lines from the shorter of the two parallel sides perpendicular so as to intersect the other longer parallel line in two places, thus dividing the trapezoid into two triangles and a rectangle. The rectangle then obviously can be divided into three portions of the same size by drawing two additional lines, all of which is shown in the drawing on a larger scale and in dotted lines only. In the hereto attached claims the area within the upper apex of the trapezoid refers to the area within such upper triangle the area within the lower apex of the trapezoid refers to such lower triangle. The area in the center of the trapezoid refers to the area defined by the middle rectangle. The area of one rectangle is defined by being between the upper apex and the center rectangle, and the other by being between the lower apex and the center rectangle, all of which is perfectly plain by reference to the drawing. An attempt to draw additional lines and to number them in the same trapezoid A, B, D, C, would only tend towards confusion and thus the present means is being employed to point out the various areas which, in turn, appear in the sub-generic claims hereto appended. Thus in the drawing, the area designated V corresponds to the area within the upper triangle, the area W corresponds to the area within the lower triangle, the area X corresponds to that of the middle rectangle, and the areas Y and Z correspond to those of the other rectangles.

Having thus described our invention what we claim as new and desire to obtain by Letters Patent is:

1. The cogeneric mixture of a homologous series of glycol ethers of N-methylglucamine; said cogeneric mixture being derived exclusively from N-methylglucamine, propylene oxide and ethylene oxide in such wei ht proportion so the average compositions of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum N-methylglucamine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines A, B, F, E.

2. The cogeneric mixture of a homologous series of glycol ethers of N-methylglucamine; said cogeneric mixture being derived exclusively from N-methylglucamine,

propylene oxide and ethylene oxide in such weight propor-' tion so the average compositions of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum N-methylglucamine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines A, B, D, C.

3. The cogeneric mixture of claim 2 with the proviso that the reactant composition approximates a point in the area corresponding with V within the upper apex of the trapezoid A, B, D, C.

4. The cogeneric mixture of claim 2 with the proviso that the reactant composition approximates a point in the area corresponding with W within the lower apex of the trapezoid A, B, D, C.

5. The cogeneric mixture of claim 2 with the proviso that the reactant composition approximates a point in the area corresponding with X of the central part of the trapezoid A, B, D, C.

6. The cogeneric mixture of claim 2 with the proviso that the reactant composition approximates a point in the area corresponding with Y between the central part of the trapezoid A, B, D, C, and the upper apex.

7. The cogeneric mixture of claim 2 with the proviso that the reactant composition approximates a point in the area corresponding with Z between the central part of the trapezoid A, B, D, C, and the lower apex.

References Cited in the file of this patent UNITED STATES PATENTS 2,489,310 Moss Nov. 29, 1949 2,574,541 De Groote et al Nov. 13, 1951 2,813,092 Zech Nov. 12, 1957 

1. THE COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF N-METHYLGLUCAMINE; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM N-METHYLGLUCAMINE, PROPYLENE OXIDE AND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTION SO THE AVERAGE COMPOSITIONS OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE TRAPEZOID OF THE ACCOMPANYING DRAWING IN 